Zhu Jiawei, Cui Tong, Chi Jingqi, Wang Tiantian, Guo Lili, Liu Xiaobin, Wu Zexing, Lai Jianping, Wang Lei
Key Laboratory of Eco-chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemical Engineering, Qingdao University of Science and Technology, 266042, Qingdao, PR China.
College of Chemical and Chemical Engineering, China University of Petroleum (East China), 266580, Qingdao, Shandong, PR China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414721. doi: 10.1002/anie.202414721. Epub 2024 Nov 9.
The development of oxygen evolution reaction (OER) electrocatalyst for seawater electrolysis plays a crucial role in producing renewable hydrogen energy. However, during the seawater electrolysis process, the anode inevitably undergoes chloride oxidation reaction (ClOR) due to Cl adsorption, making the seawater electrolysis process difficult to sustain. Inspired by the selective permeability of cell membranes, we propose a biomimetic design of frustrated Lewis pairs (FLPs) layers for selective seawater oxidation. Combining experimental results and molecular dynamics simulations, it has been demonstrated that cerium dioxide layers with FLPs sites can decompose water molecules, capture hydroxyl anions, and repel chloride ions simultaneously. DFT theoretical analysis indicates that the FLP sites regulate the Ce 4 f-O 2p-Ni 3d gradient orbital coupling, providing additional oxygen non-bonding (O) to stabilize the Ni-O bond and optimize the adsorption strength of intermediates, thereby breaking the *OH and *OOH scaling relationship. The assembled anion exchange membrane electrolyzers exhibit an efficiency of 95.7 % at a current density of 0.1 A cm and can stably operate for 250 hours at a current density of 0.2 A cm.
用于海水电解的析氧反应（OER）电催化剂的开发在生产可再生氢能方面起着至关重要的作用。然而，在海水电解过程中，由于Cl的吸附，阳极不可避免地会发生氯化物氧化反应（ClOR），这使得海水电解过程难以持续。受细胞膜选择性渗透性的启发，我们提出了一种用于选择性海水氧化的受阻路易斯对（FLPs）层的仿生设计。结合实验结果和分子动力学模拟，已证明具有FLPs位点的二氧化铈层可以分解水分子、捕获氢氧根阴离子并同时排斥氯离子。DFT理论分析表明，FLP位点调节Ce 4f-O 2p-Ni 3d梯度轨道耦合，提供额外的氧非键合（O）以稳定Ni-O键并优化中间体的吸附强度，从而打破OH和OOH的标度关系。组装的阴离子交换膜电解槽在电流密度为0.1 A cm时表现出95.7%的效率，并且在电流密度为0.2 A cm时可以稳定运行250小时。
